TW202138411A - Initiated chemical vapor deposition and structuration of polyoxymethylene - Google Patents

Initiated chemical vapor deposition and structuration of polyoxymethylene Download PDF

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TW202138411A
TW202138411A TW110104634A TW110104634A TW202138411A TW 202138411 A TW202138411 A TW 202138411A TW 110104634 A TW110104634 A TW 110104634A TW 110104634 A TW110104634 A TW 110104634A TW 202138411 A TW202138411 A TW 202138411A
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家信 劉
正韜 陳
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崔克瑟大學
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    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
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    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/46—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for heating the substrate
    • C23C16/463—Cooling of the substrate
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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/48—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating by irradiation, e.g. photolysis, radiolysis, particle radiation
    • C23C16/481—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating by irradiation, e.g. photolysis, radiolysis, particle radiation by radiant heating of the substrate
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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/52—Controlling or regulating the coating process
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/04—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases
    • B05D3/0486—Operating the coating or treatment in a controlled atmosphere

Abstract

This invention relates to a method for synthesizing polyoxymethylene on a substrate. The method includes depositing a monomer capable of forming polyoxymethylene by an initiated polymerization reaction and an initiator, via initiated chemical vapor deposition (iCVD) onto a surface of a substrate in an initiated chemical vapor deposition reactor.

Description

聚甲醛之起始化學氣相沉積及結構化Initial chemical vapor deposition and structuring of polyoxymethylene

本發明係關於一種用於在基板上合成聚甲醛之方法。The present invention relates to a method for synthesizing polyoxymethylene on a substrate.

19世紀20年代，Hermann Staudinger首次發現且深入研究聚甲醛(POM)1 - 2 。POM係一種極其受歡迎的柴油燃料添加劑，其可減少有害廢氣3 。POM亦廣泛地用作金屬及合金之替代品，諸如在機械齒輪中4 ，因為其具有高機械強度、及耐磨損性及耐疲勞性5 。POM之一個獨特態樣係其能夠乾淨地熱解聚之能力，此使得其成為用於製造暫態電子裝置6 、微機電系統(MEMS)及微流體之有吸引力的犧牲材料7 。1820s, Hermann Staudinger was first discovered and in-depth study of POM (POM) 1 - 2. An extremely popular POM-based diesel fuel additive, which may reduce harmful exhaust gases 3. POM is also widely used as a substitute for metals and alloys, such as 4 in a mechanical gear, because it has high mechanical strength, and wear resistance and fatigue resistance 5. POM a unique aspect of the system which is capable of cleanly depolymerization in thermal capacity, so that this becomes a transient sacrificial material 6 of the electronic device, microelectromechanical system (MEMS) and microfluidics 7 of attractive.

隨著裝置之尺寸縮小，由於強液體表面張力，習知以液體為基礎之聚合可潛在性地損傷裝置之易碎微結構/奈米結構。聚合期間使用的溶劑亦很難移除或留下殘留物。此係由於POM不溶於常用溶劑，因此，將POM液體加工成膜及塗層具有挑戰性。已報導用於合成POM之無溶劑方法，諸如熱燈絲化學氣相沉積(HFCVD)。經由HFCVD進行聚合需要極端條件，利用高燈絲溫度(~700℃)以分解三噁烷單體及使用液氮(＜ –195℃)以冷卻聚合物生長之階段，此可潛在性地損傷易碎基板材料及結構7 。As the size of the device shrinks, due to the strong liquid surface tension, conventional liquid-based polymerization can potentially damage the fragile microstructure/nanostructure of the device. Solvents used during polymerization are also difficult to remove or leave residues. Since POM is not soluble in common solvents, it is challenging to process POM liquid into films and coatings. Solvent-free methods for synthesizing POM have been reported, such as hot filament chemical vapor deposition (HFCVD). Polymerization via HFCVD requires extreme conditions. High filament temperature (~700℃) is used to decompose trioxane monomer and liquid nitrogen (< -195℃) is used to cool the polymer growth stage, which can potentially damage and fragile Substrate material and structure 7 .

本發明之另外細節及優點將在隨後的描述中部分地闡述，及/或可藉由本發明之實踐而獲知。本發明之細節及優點可藉助於隨附申請專利範圍中特別指出的要素及組合來實現或達成。應明瞭，前述一般描述及以下詳細描述均僅係例示性及說明性的且不限制所主張的本發明。Additional details and advantages of the present invention will be partially explained in the following description, and/or can be learned through the practice of the present invention. The details and advantages of the present invention can be realized or achieved by means of the elements and combinations specifically pointed out in the scope of the appended application. It should be understood that the foregoing general description and the following detailed description are only exemplary and illustrative and do not limit the claimed invention.

以下語句可用於描述本發明之某些實施例。The following sentences can be used to describe some embodiments of the present invention.

1. 在第一態樣中，本發明係關於一種用於在基板上合成聚甲醛(POM)之方法。該方法包括在起始化學氣相沉積反應器中將引發劑及能夠藉由起始聚合反應形成聚甲醛之單體經由起始化學氣相沉積(iCVD)沉積至基板之表面上之步驟。1. In the first aspect, the present invention relates to a method for synthesizing polyoxymethylene (POM) on a substrate. The method includes a step of depositing an initiator and a monomer capable of forming polyoxymethylene through an initial polymerization reaction on the surface of a substrate through initial chemical vapor deposition (iCVD) in an initial chemical vapor deposition reactor.

2. 在如語句1之方法中，可將該基板冷卻至低於該單體及該引發劑之沸騰溫度之溫度以促進該單體及引發劑在該基板上之沉積。2. In the method as in sentence 1, the substrate can be cooled to a temperature lower than the boiling temperature of the monomer and the initiator to promote the deposition of the monomer and the initiator on the substrate.

3. 在如語句2之方法中，可將該基板冷卻至約0℃至約50℃、或約0℃至約40℃、約10℃至約35℃或約15℃至約25℃之溫度。3. In the method as in sentence 2, the substrate can be cooled to a temperature of about 0°C to about 50°C, or about 0°C to about 40°C, about 10°C to about 35°C, or about 15°C to about 25°C .

4. 在如語句1至3中任一語句之方法中，該起始化學氣相沉積反應器中之內部反應器壓力可為約0.1至約10托，使用壓力計例如電容式壓力計測得，或約0.5至約5托、或約1至約3托。4. In the method of any one of sentences 1 to 3, the internal reactor pressure in the initial chemical vapor deposition reactor can be about 0.1 to about 10 Torr, measured by a pressure gauge such as a capacitive pressure gauge, Or about 0.5 to about 5 Torr, or about 1 to about 3 Torr.

5. 在如語句1至4中任一語句之方法中，該沉積步驟可以單體流入起始化學氣相沉積反應器之約0.1至約20標準立方厘米/分鐘(sccm)、或約2至約15 sccm、或約3至約10 sccm之流速進行。5. In the method of any one of sentences 1 to 4, the deposition step can be about 0.1 to about 20 standard cubic centimeters per minute (sccm), or about 2 to about 20 standard cubic centimeters per minute (sccm), or about 2 to about 20 standard cubic centimeters per minute (sccm) of the monomer flowing into the initial chemical vapor deposition reactor. It is performed at a flow rate of about 15 sccm, or about 3 to about 10 sccm.

6. 在如語句1至5中任一語句之方法中，該引發劑可選自由三氟化硼合***(boron trifluoride diethyl etherate)、三氟化硼及其他三氟化硼錯合物組成之群，其他三氟化硼錯合物包括與水、苯酚、乙酸、四氫呋喃、甲醇、丙醇、乙胺、甲基硫醚及二丁醚錯合之三氟化硼。6. In the method of any one of sentences 1 to 5, the initiator can be selected from boron trifluoride diethyl etherate, boron trifluoride and other boron trifluoride complexes. Group, other boron trifluoride complexes include boron trifluoride complexed with water, phenol, acetic acid, tetrahydrofuran, methanol, propanol, ethylamine, methyl sulfide and dibutyl ether.

7. 在如語句1至6中任一語句之方法中，該引發劑可在將該引發劑進料至起始化學氣相沉積反應器之前加熱至30℃至50℃、或30℃至40℃、或約35℃之溫度。7. In the method of any one of sentences 1 to 6, the initiator may be heated to 30°C to 50°C, or 30°C to 40°C before feeding the initiator to the initial chemical vapor deposition reactor. ℃, or a temperature of about 35℃.

8. 在如語句1至7中任一語句之方法中，該引發劑可以約0.1至10標準立方厘米/分鐘(sccm)、或約0.5至7.5 sccm、或約1至5 sccm之流速進料至起始化學氣相沉積反應器。8. In the method of any one of sentences 1 to 7, the initiator can be fed at a flow rate of about 0.1 to 10 standard cubic centimeters per minute (sccm), or about 0.5 to 7.5 sccm, or about 1 to 5 sccm To the starting chemical vapor deposition reactor.

9. 在如語句1至8中任一語句之方法中，該基板可選自矽、玻璃、織物、紙、塑膠、藥品、金屬、金屬氧化物、離子液體，及包含結構化、模板化、機製及界定拓撲中之一者或多者之表面及裝置。9. In the method of any one of sentences 1 to 8, the substrate can be selected from silicon, glass, fabric, paper, plastic, medicine, metal, metal oxide, ionic liquid, and includes structured, templated, Mechanisms and surfaces and devices that define one or more of the topologies.

10. 在如語句1至9中任一語句之方法中，該沉積步驟可利用位於起始化學氣相沉積反應器中之一或多個經加熱燈絲來進行。10. In the method of any one of sentences 1 to 9, the deposition step can be performed using one or more heated filaments located in the initial chemical vapor deposition reactor.

11. 在如語句10之方法中，該一或多個燈絲可為磷青銅燈絲導線。11. In the method as in sentence 10, the one or more filaments can be phosphor bronze filament wires.

12. 在如語句10至11中任一語句之方法中，可將該燈絲加熱至約150℃至400℃、或約200℃至約375℃、或約250℃至約350℃之溫度。12. In the method of any one of sentences 10 to 11, the filament can be heated to a temperature of about 150°C to 400°C, or about 200°C to about 375°C, or about 250°C to about 350°C.

13. 在如語句1至12中任一語句之方法中，該方法可進一步包括將氮氣引入至反應器中之步驟。13. In the method of any one of sentences 1 to 12, the method may further include the step of introducing nitrogen into the reactor.

14. 在如語句13之方法中，該氮氣可以0.1 sccm至約2 sccm之流速、或約1 sccm之流速引入至反應器中。14. In the method as in clause 13, the nitrogen gas can be introduced into the reactor at a flow rate of 0.1 sccm to about 2 sccm, or a flow rate of about 1 sccm.

15. 在如語句1至14中任一語句之方法中，該單體可選自由1,3,5-三噁烷、甲醛、二噁烷、可形成甲醛及其寡聚物之其他環分子諸如較大(CH2 O)含環分子，及已知用於聚合反應中以形成聚甲醛之其他單體，諸如線性或環狀形式之具有2至100個重複基團之POM之聚合物，以及二噁烷、三噁烷及多聚甲醛組成之群。15. In the method of any one of sentences 1 to 14, the monomer can be selected from 1,3,5-trioxane, formaldehyde, dioxane, and other ring molecules that can form formaldehyde and its oligomers Such as larger (CH 2 O) ring-containing molecules, and other monomers known to be used in polymerization reactions to form polyoxymethylene, such as polymers of POM with 2 to 100 repeating groups in linear or cyclic form, And the group consisting of dioxane, trioxane and paraformaldehyde.

16. 在如語句1至15中任一語句之方法中，該沉積步驟可在使得基板表面處1,3,5-三噁烷單體之分數飽和度(

Figure 02_image001
)通常在0.1至約1之間之條件下進行，其中
Figure 02_image001
係由以下表達式定義：
Figure 02_image003
其中
Figure 02_image005
為氣相中單體之分壓，基於透過精密針閥或質量流量控制器計量的組分流速及透過壓力計例如電容式壓力計測得之反應器總壓力計算得，及
Figure 02_image007
為基板表面處單體之蒸氣壓，基於單體在表面溫度下之平衡蒸氣壓數據，藉由表面溫度探針，例如接觸熱電偶測得。16. In the method of any one of sentences 1 to 15, the deposition step may be such that the fractional saturation of the 1,3,5-trioxane monomer at the surface of the substrate (
Figure 02_image001
) Is usually carried out under conditions between 0.1 and about 1, where
Figure 02_image001
Is defined by the following expression:
Figure 02_image003
in
Figure 02_image005
It is the partial pressure of the monomer in the gas phase, calculated based on the component flow rate measured by a precision needle valve or mass flow controller and the total reactor pressure measured by a pressure gauge such as a capacitive pressure gauge, and
Figure 02_image007
It is the vapor pressure of the monomer at the surface of the substrate, based on the equilibrium vapor pressure data of the monomer at the surface temperature, measured by a surface temperature probe, such as a contact thermocouple.

17. 在如語句1至16中任一語句之方法中，該方法可進一步包括引入一或多種選自水、醇及醛之共反應物之步驟。17. In the method of any one of sentences 1 to 16, the method may further include the step of introducing one or more co-reactants selected from water, alcohol and aldehyde.

18. 在如語句17之方法中，該共反應物可為甲醇。甲醇可以約0.1至約2 sccm、或約0.1至約1 sccm之流速引入至反應器中。18. In the method as in clause 17, the co-reactant can be methanol. Methanol can be introduced into the reactor at a flow rate of about 0.1 to about 2 sccm, or about 0.1 to about 1 sccm.

19. 在如語句17之方法中，該共反應物可為多聚甲醛。可將該多聚甲醛加熱至60℃- 120℃且以約0.1 sccm至約2 sccm、或約0.1 sccm至約2 sccm之蒸氣流速進料。19. In the method as in sentence 17, the co-reactant can be paraformaldehyde. The paraformaldehyde can be heated to 60°C to 120°C and fed at a vapor flow rate of about 0.1 sccm to about 2 sccm, or about 0.1 sccm to about 2 sccm.

20. 在如語句1至17中任一語句之方法中，該方法可進一步包括引入水作為共反應物之步驟。20. In the method of any one of sentences 1 to 17, the method may further include the step of introducing water as a co-reactant.

相關申請案之交叉參考Cross reference of related applications

本申請案主張2020年2月13日申請之美國臨時申請案第62/975,866號之權益，其全部揭示內容係以引用之方式併入本文中，如同在本文中完全闡述般。This application claims the rights and interests of U.S. Provisional Application No. 62/975,866 filed on February 13, 2020, and the entire disclosure of which is incorporated herein by reference, as if it were fully described in this article.

為解決與POM相關之挑戰，本發明方法引入替代無溶劑方法、起始化學氣相沉積(iCVD)，以用於建立POM。iCVD蒸發液體前驅物，通常係單體及引發劑，以在各種基板上直接合成固體聚合物，像POM。藉由與液相分配，iCVD克服較差潤濕性及通常與液體溶劑相關之基板損傷。另外，使用聚合引發劑可顯著降低燈絲溫度(250至350℃)且提供室溫表面聚合，此可允許使用易碎基板，包括織物、紙、塑膠、藥品、金屬、金屬氧化物及離子液體。In order to solve the challenges related to POM, the method of the present invention introduces an alternative solvent-free method, initial chemical vapor deposition (iCVD), for the establishment of POM. iCVD evaporates liquid precursors, usually monomers and initiators, to directly synthesize solid polymers on various substrates, like POM. By distributing with the liquid phase, iCVD overcomes poor wettability and substrate damage usually associated with liquid solvents. In addition, the use of polymerization initiators can significantly reduce the filament temperature (250 to 350°C) and provide room temperature surface polymerization, which allows the use of fragile substrates, including fabrics, paper, plastics, pharmaceuticals, metals, metal oxides, and ionic liquids.

在沉積之前，可將該基板冷卻至某一溫度以促進單體及引發劑在基板上之沉積。可將該基板冷卻至約0℃至約50℃、或約0℃至約40℃、或約10℃至約35℃、或約15℃至約25℃之溫度。基板之適宜實例可包括矽、玻璃織物、紙、塑膠、藥品、金屬、金屬氧化物、離子液體，及包含結構化、模板化、機製及界定拓撲中之一者或多者之表面及裝置。Before deposition, the substrate can be cooled to a certain temperature to promote the deposition of monomer and initiator on the substrate. The substrate can be cooled to a temperature of about 0°C to about 50°C, or about 0°C to about 40°C, or about 10°C to about 35°C, or about 15°C to about 25°C. Suitable examples of substrates may include silicon, glass fabric, paper, plastics, pharmaceuticals, metals, metal oxides, ionic liquids, and surfaces and devices that include one or more of structured, templating, mechanism, and defined topology.

具體而言，iCVD仰賴於在低/中真空腔室(1×10-3 至760托)中連續傳遞蒸發的引發劑及單體，其中該引發劑係通過藉由任何適宜方式，諸如藉由使用經加熱燈絲之陣列進行加熱來選擇性活化，該經加熱燈絲之陣列懸浮於經冷卻之所關注的基板之上，其促進經活化引發劑及單體之吸附，此然後導致表面聚合8-9 。儘管自由基聚合已藉由iCVD成功用於合成多種聚合物，但陽離子開環聚合已被證明可用於合成聚環氧乙烷(PEO)10 及聚縮水甘油(PGL)11 (藉由分別使用環氧乙烷及乙二醇單體)、及陽離子引發劑三氟化硼合***(BF3 ·O(C2 H5 )2 )。Specifically, iCVD relies on the continuous transfer of evaporated initiator and monomer in a low/medium vacuum chamber (1×10 -3 to 760 Torr), where the initiator is passed by any suitable means, such as by Selective activation is performed by heating using an array of heated filaments suspended on the cooled substrate of interest, which promotes the adsorption of activated initiators and monomers, which then leads to surface polymerization 8- 9 . Although free radical polymerization has been successfully used to synthesize a variety of polymers by iCVD, cationic ring-opening polymerization has been proven to be useful for the synthesis of polyethylene oxide (PEO) 10 and polyglycidol (PGL) 11 (by using ring Oxyethane and ethylene glycol monomer), and cationic initiator boron trifluoride ether (BF 3 ·O(C 2 H 5 ) 2 ).

起始化學氣相沉積反應器中之內部反應器壓力可為約0.01至約100托、或約0.1至約10托、或約0.5至約5托、或約1至約3托，使用壓力計，例如電容式壓力計測得。The internal reactor pressure in the initial chemical vapor deposition reactor can be about 0.01 to about 100 Torr, or about 0.1 to about 10 Torr, or about 0.5 to about 5 Torr, or about 1 to about 3 Torr, using a pressure gauge , Such as measured by a capacitive pressure gauge.

在本發明中，iCVD可用於使用單體及引發劑之任何適宜組合來合成聚甲醛(POM)。適宜單體為已知用於聚合反應中以產生POM之彼等單體，諸如1,3,5-三噁烷單體、甲醛、二噁烷、可在iCVD反應器中形成甲醛且其寡聚物之較大(CH2 O)含環單體及用於經由起始聚合製備POM之其他適宜單體。該沉積步驟可以單體流入起始化學氣相沉積反應器之約0.1至約20標準立方厘米/分鐘(sccm)、或約2至約15 sccm、或約3至約10 sccm之流速進行。In the present invention, iCVD can be used to synthesize polyoxymethylene (POM) using any suitable combination of monomers and initiators. Suitable monomers are those known to be used in polymerization reactions to produce POM, such as 1,3,5-trioxane monomers, formaldehyde, dioxane, formaldehyde that can be formed in iCVD reactors, and their oligomers. The larger (CH 2 O) ring-containing monomer of the polymer and other suitable monomers for preparing POM via initial polymerization. The deposition step can be carried out at a flow rate of about 0.1 to about 20 standard cubic centimeters per minute (sccm), or about 2 to about 15 sccm, or about 3 to about 10 sccm at which the monomer flows into the initial chemical vapor deposition reactor.

在一些實施例中，該沉積步驟係在使得基板表面處1,3,5-三噁烷單體之分數飽和度(

Figure 02_image001
)為0.1至約1之條件下進行，其中
Figure 02_image001
係由以下表達式定義：
Figure 02_image009
其中
Figure 02_image005
為氣相中單體之分壓，如基於透過精密針閥或質量流量控制器計量的組分流速及透過壓力計(例如電容式壓力計)測得之反應器總壓力計算得，及
Figure 02_image007
為基板表面處單體之蒸氣壓，基於單體在如藉由表面溫度探針(例如接觸熱電偶)測得之基板溫度下之平衡蒸氣壓數據。
Figure 02_image005
可使用公式
Figure 02_image005
= ym *P = (Fm /Ftot )*P進行估算，其中ym 為氣相中單體之莫耳分率及P為如藉由壓力計測得之總反應器壓力。ym 可基於單體之莫耳流速與總莫耳流速之比(Fm /Ftot )來計算得，此等流速係由流量校準測量獲得。
Figure 02_image011
為基板表面處單體之蒸氣壓或飽和壓力且係基於來自公開文獻之平衡壓力數據與溫度之熱力學關係(例如Antoine或van’t Hoff方程式)來估算。In some embodiments, the deposition step is to make the fractional saturation of the 1,3,5-trioxane monomer at the surface of the substrate (
Figure 02_image001
) Is carried out under the condition of 0.1 to about 1, wherein
Figure 02_image001
Is defined by the following expression:
Figure 02_image009
in
Figure 02_image005
It is the partial pressure of the monomer in the gas phase, such as calculated based on the component flow rate measured by a precision needle valve or mass flow controller and the total pressure of the reactor measured by a pressure gauge (such as a capacitive pressure gauge), and
Figure 02_image007
It is the vapor pressure of the monomer at the surface of the substrate, based on the equilibrium vapor pressure data of the monomer at the substrate temperature as measured by a surface temperature probe (such as a contact thermocouple).
Figure 02_image005
Available formula
Figure 02_image005
= y m *P = (F m /F tot )*P for estimation, where y m is the molar fraction of monomer in the gas phase and P is the total reactor pressure as measured by a pressure gauge. y m can be calculated based on the ratio of the molar flow rate of the monomer to the total molar flow rate (F m /F tot ), and these flow rates are obtained by flow calibration measurement.
Figure 02_image011
It is the vapor pressure or saturation pressure of the monomer at the surface of the substrate and is estimated based on the thermodynamic relationship between equilibrium pressure data and temperature (for example, Antoine or van't Hoff equation) from public literature.

適宜引發劑為彼等已知用於單體之聚合以產生POM者且尤佳引發劑為能夠使用包含一或多個環狀環之單體進行陽離子開環聚合反應之引發劑。適宜引發劑包括，但不限於，路易斯酸(Lewis acid) (諸如三氟化硼合***、三氟化硼及其他三氟化硼錯合物，包括與水、苯酚、乙酸、四氫呋喃、甲醇、丙醇、乙胺、甲基硫醚及二丁醚錯合之三氟化硼)、其他金屬鹵化物(諸如AlCl3 、AlBr3 、TiCl4 、SnCl4 )、以及其有機金屬變體(像RAlCl2 、R2 AlCl及R3 Cl，其中R為烷基或芳基基團)。在將引發劑進料至起始化學氣相沉積反應器之前，可將引發劑加熱至約28℃至約50℃、或約30℃至50℃、或30℃至40℃、或約35℃之溫度。可將引發劑以約0.05至10標準立方厘米/分鐘(sccm)、或約0.1 sccm至約10 sccm、或約0.5至7.5 sccm、或約1至5 sccm之流速進料至起始化學氣相沉積反應器。Suitable initiators are those known to be used in the polymerization of monomers to produce POM and particularly preferred initiators are those that can perform cationic ring-opening polymerization using monomers containing one or more cyclic rings. Suitable initiators include, but are not limited to, Lewis acid (such as boron trifluoride ether, boron trifluoride and other boron trifluoride complexes, including water, phenol, acetic acid, tetrahydrofuran, methanol, Propanol, ethylamine, methyl sulfide and dibutyl ether complexed with boron trifluoride), other metal halides (such as AlCl 3 , AlBr 3 , TiCl 4 , SnCl 4 ), and their organometallic variants (like RAlCl 2 , R 2 AlCl and R 3 Cl, where R is an alkyl or aryl group). Before feeding the initiator to the initial chemical vapor deposition reactor, the initiator may be heated to about 28°C to about 50°C, or about 30°C to 50°C, or 30°C to 40°C, or about 35°C的温度。 The temperature. The initiator can be fed to the starting chemical gas phase at a flow rate of about 0.05 to 10 standard cubic centimeters per minute (sccm), or about 0.1 sccm to about 10 sccm, or about 0.5 to 7.5 sccm, or about 1 to 5 sccm Deposition reactor.

在一些實施例中，沉積步驟係用位於起始化學氣相沉積反應器中的一或多個經加熱燈絲進行。該一或多個燈絲之適宜實例可選自磷青銅、銅、鈹銅、鎳、Chromaloy™、鎳鉻合金(Nichrome)、不銹鋼、鐵及其他適宜金屬或金屬合金燈絲導線。可將一或多個燈絲加熱至約150℃至約400℃、或約200℃至約375℃、或約250℃至約350℃之溫度。在一些實施例中，該方法可進一步包括將氮氣引入至反應器中之步驟。較佳地，氮氣係以約0.1 sccm至約2 sccm之流速或約1 sccm之流速引入至反應器中。In some embodiments, the deposition step is performed with one or more heated filaments located in the initial chemical vapor deposition reactor. Suitable examples of the one or more filaments can be selected from phosphor bronze, copper, beryllium copper, nickel, Chromaloy™, Nichrome, stainless steel, iron, and other suitable metal or metal alloy filament wires. One or more filaments can be heated to a temperature of about 150°C to about 400°C, or about 200°C to about 375°C, or about 250°C to about 350°C. In some embodiments, the method may further include the step of introducing nitrogen into the reactor. Preferably, nitrogen gas is introduced into the reactor at a flow rate of about 0.1 sccm to about 2 sccm or about 1 sccm.

例如，使用1,3,5-三噁烷單體及三氟化硼合***(BF3 ·O(C2 H5 )2 )引發劑，POM聚合物膜可經由iCVD來製成。iCVD係用於在三氟化硼引發劑存在下使三噁烷單體進行陽離子開環聚合以合成POM。iCVD加工條件可透過一個關鍵參數(即基板表面處單體之分數飽和度(z =P M /P M,sat )，其本質上測定表面單體濃度)來控制以影響iCVD聚合動力學。此z 參數直接受化學前驅物流速、惰性載氣流速、真空腔室之總壓力、燈絲溫度及基板溫度的影響。藉由控制iCVD同步沉積條件，可在提供高表面單體濃度之條件下成功生長POM。再者，iCVD合成導致在三角形晶體結構之六角形堆積中形成主要POM之延展晶體鏈形式。iCVD生長期間POM之結晶導致POM膜之結構化。所得的結構化POM將潤濕性自緻密POM之親水性表面轉移至結構化POM之疏水性表面。For example, using 1,3,5-trioxane monomer and boron trifluoride ether (BF 3 ·O(C 2 H 5 ) 2 ) initiator, the POM polymer film can be made by iCVD. iCVD system is used for cationic ring-opening polymerization of trioxane monomer in the presence of boron trifluoride initiator to synthesize POM. iCVD through a critical processing parameter conditions (i.e., fraction of monomer of saturation of the substrate surface (z = P M / P M , sat), which is essentially measuring the surface concentration of the monomer) to effect controlled iCVD polymerization kinetics. This z parameter is directly affected by the flow rate of the chemical precursor, the flow rate of the inert carrier gas, the total pressure of the vacuum chamber, the temperature of the filament and the temperature of the substrate. By controlling the simultaneous deposition conditions of iCVD, POM can be successfully grown under conditions that provide high surface monomer concentration. Furthermore, iCVD synthesis results in the formation of extended crystal chain forms of the main POM in the hexagonal packing of the triangular crystal structure. The crystallization of POM during iCVD growth leads to the structuring of the POM film. The resulting structured POM transfers the wettability from the hydrophilic surface of the dense POM to the hydrophobic surface of the structured POM.

在一些實施例中，該方法可包括引入一或多種選自水、醇及醛及其混合物之共反應物之步驟。醇之適宜實例可包括甲醇、乙醇、異丙醇、1-丁醇、1-己醇、1-癸醇、丙-2醇、乙二醇、1,2-丙二醇、烷氧基醇、烷基醇，較佳使用甲醇。醛之適宜實例可包括甲醛、多聚甲醛、三噁烷、乙醛、乙二醛、戊二醛、聚甲醛、丙醛、異丁醛、苯甲醛。較佳地，醛為多聚甲醛。In some embodiments, the method may include the step of introducing one or more co-reactants selected from water, alcohol, and aldehyde, and mixtures thereof. Suitable examples of alcohols may include methanol, ethanol, isopropanol, 1-butanol, 1-hexanol, 1-decanol, propan-2 alcohol, ethylene glycol, 1,2-propanediol, alkoxy alcohol, alkane Base alcohol, methanol is preferably used. Suitable examples of aldehydes may include formaldehyde, paraformaldehyde, trioxane, acetaldehyde, glyoxal, glutaraldehyde, polyformaldehyde, propionaldehyde, isobutyraldehyde, benzaldehyde. Preferably, the aldehyde is paraformaldehyde.

在其中使用醇作為共反應物之實施例中，可將醇以約0.1至約2 sccm、或約0.1至約1 sccm之流速引入至反應器中。在其他實施例中，在使用醛作為共反應物之情況下，例如，若醛為多聚甲醛，則將多聚甲醛加熱至60℃至120℃以達成約0.1 sccm至約2 sccm、或約0.1 sccm至約2 sccm之蒸氣流速。1. 實驗部分 In embodiments where alcohol is used as the co-reactant, the alcohol may be introduced into the reactor at a flow rate of about 0.1 to about 2 sccm, or about 0.1 to about 1 sccm. In other embodiments, when an aldehyde is used as the co-reactant, for example, if the aldehyde is paraformaldehyde, the paraformaldehyde is heated to 60°C to 120°C to achieve about 0.1 sccm to about 2 sccm, or about Vapor flow rate from 0.1 sccm to about 2 sccm. 1. Experimental part

iCVD 裝置 。 使用21×21×4 cm3 大小的具有2.5-cm厚石英窗蓋之定製iCVD反應器以生長POM。基板為矽晶圓(直徑為100 mm，Pure Wafer)，且放置於反應器台上，藉由與流過再循環冷卻器(Polyscience 912)之熱流體背側接觸而冷卻以將基板溫度控制在0℃與25℃之間。將K型熱電偶連接至基板之頂表面以測定溫度。HeNe雷射用於監測聚合物膜在基板上之原位生長。對於POM合成而言獨特的是，可在存在或不存在經加熱燈絲下引發聚合物生長。若使用燈絲，則將一組12個磷青銅燈絲導線(0.5 mm直徑，Goodfellow)放置於基板上方2 cm處。為將燈絲加熱高達~330℃，將導線連接至設定為10.5 V (4 A)之恆定電壓之DC電源(Vol Teq)。使用Edwards旋轉真空泵(E2M30)、Baratron電容式壓力計(MKS 626C)及下游節流閥(MKS 153D)以將反應器腔室內部的設定壓力自動維持在1托與3托之間。 iCVD device . A custom iCVD reactor with a size of 21×21×4 cm 3 with a 2.5-cm thick quartz window cover was used to grow POM. The substrate is a silicon wafer (100 mm in diameter, Pure Wafer), which is placed on the reactor stage and cooled by contact with the back side of the thermal fluid flowing through the recirculation cooler (Polyscience 912) to control the substrate temperature at Between 0°C and 25°C. Connect a K-type thermocouple to the top surface of the substrate to measure the temperature. HeNe laser is used to monitor the in-situ growth of polymer film on the substrate. Unique to POM synthesis is that polymer growth can be initiated in the presence or absence of heated filaments. If a filament is used, a set of 12 phosphor bronze filament wires (0.5 mm diameter, Goodfellow) are placed 2 cm above the substrate. In order to heat the filament up to ~330°C, connect the wire to a constant voltage DC power supply (Vol Teq) set to 10.5 V (4 A). Edwards rotary vacuum pump (E2M30), Baratron capacitive pressure gauge (MKS 626C) and downstream throttle valve (MKS 153D) were used to automatically maintain the set pressure inside the reactor chamber between 1 Torr and 3 Torr.

合成。 使用三氟化硼合***((BF3 ·O(C2 H5 )2 )，98+%，Alfa Aesar)及1,3,5-三噁烷(99.5+%，Acros Organics)分別作為陽離子引發劑及單體，而無需進一步純化。將引發劑加熱至35℃以達成足夠的頂部蒸氣壓。經由精密針閥(Swagelok)將引發劑流速設定在0.1 sccm與2 sccm (標準立方厘米/分鐘)之間。使用單獨精密針閥(Swagelok)將單體加熱至40℃，且將單體流速設定在3 sccm與10 sccm之間。氮氣載氣(0至2 sccm)藉由自動質量流量控制器(MKS 1479A)控制。引發劑、單體及氮氣經由經加熱之0.25英寸直徑的不銹鋼管件傳遞至反應器。在一些反應器中，另外使用甲醇或多聚甲醛作為共反應物。將甲醇流速設定在0.1 sccm與1 sccm之間，而將多聚甲醛熱加熱至60至120℃以達成在0.1 sccm與1 sccm之間之甲醛蒸氣流速。 synthesis. Use boron trifluoride ether ((BF 3 ·O(C 2 H 5 ) 2 ), 98+%, Alfa Aesar) and 1,3,5-trioxane (99.5+%, Acros Organics) as cations Initiator and monomer without further purification. The initiator is heated to 35°C to achieve sufficient top vapor pressure. The initiator flow rate was set between 0.1 sccm and 2 sccm (standard cubic centimeters per minute) via a precision needle valve (Swagelok). A separate precision needle valve (Swagelok) was used to heat the monomer to 40°C, and the monomer flow rate was set between 3 sccm and 10 sccm. The nitrogen carrier gas (0 to 2 sccm) is controlled by an automatic mass flow controller (MKS 1479A). The initiator, monomer, and nitrogen are delivered to the reactor via heated 0.25 inch diameter stainless steel pipes. In some reactors, methanol or paraformaldehyde is additionally used as a co-reactant. The methanol flow rate is set between 0.1 sccm and 1 sccm, and the paraformaldehyde is heated to 60 to 120°C to achieve a formaldehyde vapor flow rate between 0.1 sccm and 1 sccm.

表徵。 為闡明聚合物化學結構，使用Nicolet 6700自400至4000 cm–1 以4 cm–1 解析度超過128次掃描來進行FTIR測量。為探測聚合物結晶度，在具有Cu Kα輻射(1.54 Å)且步長為0.02°之Rigaku SmartLab X射線繞射儀上進行X射線繞射(XRD)。使用掃描電子顯微術(SEM)物理表徵表面形態。為準備進行SEM分析，使用濺射塗佈機(Cressington 208 HR)在40 mA下用Pt/Pd塗佈樣品30秒以將絕緣聚合物之帶電最小化。將樣品以45°之角度定位在濺射塗佈機中，且將其連續地旋轉以確保樣品均勻地塗佈在頂部及橫截面上。SEM係在加速電壓為2至4 kV且工作距離為~5 mm之Zeiss Supra 50VP上進行。獲得基板之俯視圖及橫截面視圖。基板表面之潤濕性係藉由在接觸角測角儀(ramé-hart instrument co.)上測量幾種測試液體之接觸角來表徵且藉由DROPimage高級軟體處理。2. 結果與討論 Characterization. To clarify the chemical structure of the polymer, Nicolet 6700 was used to perform FTIR measurements from 400 to 4000 cm-1 with a resolution of 4 cm-1 over 128 scans. To detect polymer crystallinity, X-ray diffraction (XRD) was performed on a Rigaku SmartLab X-ray diffractometer with Cu Kα radiation (1.54 Å) and a step size of 0.02°. The surface morphology was physically characterized using scanning electron microscopy (SEM). To prepare for SEM analysis, a sputter coater (Cressington 208 HR) was used to coat the sample with Pt/Pd at 40 mA for 30 seconds to minimize the charging of the insulating polymer. The sample is positioned in the sputter coater at an angle of 45°, and it is continuously rotated to ensure that the sample is evenly coated on the top and cross section. SEM was performed on Zeiss Supra 50VP with an acceleration voltage of 2 to 4 kV and a working distance of ~5 mm. Obtain a top view and a cross-sectional view of the substrate. The wettability of the substrate surface is characterized by measuring the contact angle of several test liquids on a contact angle goniometer (ramé-hart instrument co.) and is processed by DROPimage advanced software. 2. Results and discussion

研究一系列iCVD加工條件以理解iCVD POM之生長窗，表 1 中所顯示。一般而言，POM在足夠高的z 條件下，亦即在存在足夠表面單體濃度之情況下生長。具體而言，此通常係在較高壓力、較低基板溫度及較低氮氣流速之較小稀釋度下。在此類條件下，沉積速率可在80 nm/min至1 µm/min之範圍內，且z 越高，生長速率越高。以往的研究已報導，三噁烷傾向於在氣相-固相及液相-固相轉變期間聚合12-13 ，且有理由懷疑該iCVD聚合僅在單體以足夠高的單體濃度吸附於基板上時進行。另外，通常在1,3,5-三噁烷在溶液中之陽離子聚合中觀測到誘導期。在此誘導期中，甲醛及其寡聚物在大分子形成之前引發後形成，且聚合僅在甲醛達到溫度依賴性最高濃度然後將反應平衡推向POM形成時開始14 。在iCVD POM中可能發生類似機制，參見圖 1 ，因此足夠高的z 或單體條件將反應推向POM生長而不是不產生固體物質之小分子或寡聚物形成。另外，POM反應可進一步受可幫助聚合物鏈引發之共反應物(通常是硫辛酸(protogen))之存在的影響。硫辛酸可例如為水或醇。因此，亦已如表 1 中所顯示進行與甲醇之反應。另外，為將平衡推向產生更多POM而不是甲醛，亦可在POM反應期間人為地引入甲醛蒸氣環境。此可藉由自多聚甲醛之熱分解引入甲醛蒸氣流來達成。亦已如表 1 中所顯示進行與甲醛之反應。該反應之提出的反應機制顯示於圖1中。表 1. POM 聚合之 iCVD 加工條件。 操作編號 引發劑流速(sccm ） 單體流速(sccm) 氮氣流速(sccm) 甲醇流速(sccm) 甲醛流速(sccm) 基板溫度(℃) 壓力( 托) 燈絲 1 1 10 0 0 0 16 3 無 2 1 3 0 0 0 16 3 無 3 2 3 0 0 0 21 3 有 4 1 3 1 0 0 21 3 有 5 1 10 0 0 0 25 3 有 6 1 3 1 0 0 21 2 有 7 1 3 0 0 0 25 3 有 8 1 3 1 0 0 25 3 有 9 1 3 1 0 0 21 1 有 10 1 3 1 0 0 29 3 有 11 1 3 1 0 0 31 1 有 12 1 3 0 0 0 11 1.25 無 13 1 3 0 0 0 8 1.25 無 14 1 3 0 0 0 5 1.25 無 15 0.85 3 0.15 0 0 8 1.25 無 16 0.70 3 0.30 0 0 8 1.25 無 17 0.85 3 0.15 0 0 8 1.25 無 18 1 2 1 0 0 8 1.25 無 19 1 1 2 0 0 8 1.25 無 20 1 3 0 0 0 8 1.10 無 21 1 3 0 0 0 8 1.40 無 22 0.70 3 0 0.30 0 8 1.25 無 23 1 3 0 1.00 0 20 1.25 無 24 1 3 0 1.00 0 18.5 1.25 無 25 1 3 0 0 1.00 8 1.25 無 26 1 3 0 1.00 0 8 1.25 無 27 1 3 1 0 0 8 1.25 無 28 1 0 0 9.00 0 8 1.25 無 29 0.7 3 0 0.30 0 8 1.25 無 30 0.5 3 0.50 0.30 0 8 1.25 無 Study a series of iCVD processing conditions to understand the growth window of iCVD POM, as shown in Table 1. Generally speaking, POM grows under sufficiently high z conditions, that is, in the presence of sufficient surface monomer concentration. Specifically, this is usually at a higher pressure, a lower substrate temperature, and a lower dilution of a lower nitrogen flow rate. Under such conditions, the deposition rate can be in the range of 80 nm/min to 1 µm/min, and the higher the z, the higher the growth rate. Previous studies have reported that tends trioxane vapor - solid phase and a liquid phase - solid phase transition 12-13 during the polymerization, and the only reason to suspect that iCVD polymerizable monomer in the monomer concentration high enough adsorbed to When on the substrate. In addition, an induction period is usually observed in the cationic polymerization of 1,3,5-trioxane in solution. During this induction period, formaldehyde and its oligomers are initiated and formed before the formation of macromolecules, and the polymerization starts only when the formaldehyde reaches the highest temperature-dependent concentration and then the reaction equilibrium is pushed toward the formation of POM14 . A similar mechanism may occur in iCVD POM, see Figure 1 , so a sufficiently high z or monomer condition pushes the reaction toward POM growth rather than the formation of small molecules or oligomers that do not produce solid matter. In addition, the POM reaction can be further affected by the presence of a co-reactant (usually lipoic acid (protogen)) that can aid in the initiation of the polymer chain. The lipoic acid can be, for example, water or alcohol. Therefore, the reaction with methanol has also proceeded as shown in Table 1. In addition, in order to push the balance to produce more POM instead of formaldehyde, the formaldehyde vapor environment can also be artificially introduced during the POM reaction. This can be achieved by introducing a stream of formaldehyde vapor from the thermal decomposition of paraformaldehyde. The reaction with formaldehyde has also proceeded as shown in Table 1. The proposed reaction mechanism of this reaction is shown in Figure 1. Table 1. iCVD processing conditions for POM polymerization. Operation number Initiator flow rate (sccm ) Monomer flow rate (sccm) Nitrogen flow rate (sccm) Methanol flow rate (sccm) Formaldehyde flow rate (sccm) Substrate temperature (℃) Pressure ( torr) filament 1 1 10 0 0 0 16 3 without 2 1 3 0 0 0 16 3 without 3 2 3 0 0 0 twenty one 3 Have 4 1 3 1 0 0 twenty one 3 Have 5 1 10 0 0 0 25 3 Have 6 1 3 1 0 0 twenty one 2 Have 7 1 3 0 0 0 25 3 Have 8 1 3 1 0 0 25 3 Have 9 1 3 1 0 0 twenty one 1 Have 10 1 3 1 0 0 29 3 Have 11 1 3 1 0 0 31 1 Have 12 1 3 0 0 0 11 1.25 without 13 1 3 0 0 0 8 1.25 without 14 1 3 0 0 0 5 1.25 without 15 0.85 3 0.15 0 0 8 1.25 without 16 0.70 3 0.30 0 0 8 1.25 without 17 0.85 3 0.15 0 0 8 1.25 without 18 1 2 1 0 0 8 1.25 without 19 1 1 2 0 0 8 1.25 without 20 1 3 0 0 0 8 1.10 without twenty one 1 3 0 0 0 8 1.40 without twenty two 0.70 3 0 0.30 0 8 1.25 without twenty three 1 3 0 1.00 0 20 1.25 without twenty four 1 3 0 1.00 0 18.5 1.25 without 25 1 3 0 0 1.00 8 1.25 without 26 1 3 0 1.00 0 8 1.25 without 27 1 3 1 0 0 8 1.25 without 28 1 0 0 9.00 0 8 1.25 without 29 0.7 3 0 0.30 0 8 1.25 without 30 0.5 3 0.50 0.30 0 8 1.25 without

操作12至30之數據類似於本文中針對於操作1至12所提供的數據。The data for operations 12 to 30 is similar to the data provided for operations 1 to 12 in this article.

圖 2 顯示1,3,5-三噁烷單體及使用及不使用經加熱燈絲沉積之iCVD POM膜之FTIR光譜。在2983及2923 cm–1 處之峰為CH2 拉伸，1470、1383及1292 cm–1 峰為CH2 彎曲、擺動及扭曲，及1239、1095及902 cm–1 峰為為POM之特性之C–O–C拉伸7 。不同於POM，單體具有2700至3100 cm–1 之更多峰及在聚合時消失的約700至8000 cm–1 之強峰7 。FTIR經由iCVD證實POM之線性結構及合成。再者，FTIR指示POM主要呈延展鏈晶體結構形式。除了FTIR外，XRD顯示在22.9°處之峰，如圖 3 中所見。此峰產生16.2 nm–1 之倒易散射向量q 及3.87 Å之d 間距，此代表POM之三角形形式之六角形陣列之(110)及(020)平面，此極其接近理論值(3.86 Å)15 。 Figure 2 shows the FTIR spectra of 1,3,5-trioxane monomer and iCVD POM film deposited with and without heated filament. The peaks at 2983 and 2923 cm –1 are CH 2 stretching, the peaks at 1470, 1383 and 1292 cm –1 are CH 2 bending, swing and twisting, and the peaks at 1239, 1095 and 902 cm –1 are characteristic of POM. C–O–C stretch 7 . Unlike POM, the monomer has more peaks from 2700 to 3100 cm -1 and strong peaks from about 700 to 8000 cm -1 that disappear during polymerization 7 . FTIR confirmed the linear structure and synthesis of POM through iCVD. Furthermore, FTIR indicates that POM is mainly in the form of extended chain crystal structure. In addition FTIR, XRD peaks appear in place of 22.9 °, as seen in FIG. This peak produces a reciprocal scattering vector q of 16.2 nm –1 and a distance of d of 3.87 Å, which represents the (110) and (020) planes of the hexagonal array of the triangular form of POM, which is very close to the theoretical value (3.86 Å) 15 .

圖 4A 至 4B 、 4D 至 4E 及 4G 至 4H 中之SEM影像顯示iCVD沉積導致結構化POM膜，此可能係由聚合製程期間之結晶引起。氮之引入及較高基板溫度均導致具有許多聚合物簇島之形態。此類結構化膜然後轉換為更具疏水性之POM表面(水接觸角 ＞ 90°)，此不同於據文獻中報導為親水性(水接觸角 = 74.5° ＜ 90°)之本體POM16 。根據吾人製程研究，操作編號5之POM膜具有最多數量之聚合物結構而導致111°之最高接觸角。 對於與甲醇及/或甲醛之反應，FTIR亦證實已沉積POM。此外，甲醇提高POM沉積之最高溫度，導致在較高基板溫度下穩定生長。而多聚甲醛改良整個基板上之沉積均勻性。3. 結論 The SEM images in FIGS. 4A to 4B , 4D to 4E, and 4G to 4H show that iCVD deposition results in a structured POM film, which may be caused by crystallization during the polymerization process. Both the introduction of nitrogen and the higher substrate temperature result in the morphology of many polymer cluster islands. This type of structured film is then converted to a more hydrophobic POM surface (water contact angle> 90°), which is different from the bulk POM 16 which is reported to be hydrophilic (water contact angle = 74.5° <90°) in the literature. According to our process research, the POM film with operation number 5 has the largest number of polymer structures, resulting in the highest contact angle of 111°. For reactions with methanol and/or formaldehyde, FTIR also confirmed that POM had been deposited. In addition, methanol increases the maximum temperature of POM deposition, resulting in stable growth at higher substrate temperatures. Paraformaldehyde improves the uniformity of deposition on the entire substrate. 3. Conclusion

經由iCVD藉由使用1,3,5-三噁烷單體及三氟化硼引發劑成功合成POM。iCVD POM膜經結構化而導致疏水性POM表面。藉由調整基板溫度、反應器壓力及氮氣流速之iCVD製程條件，可調整聚合物生長、動力學及形態。使用本發明方法易於進行POM膜之乾法合成(dry synthesis)及結構化可開拓新應用領域，包括電子、機械系統、障壁膜、模板化及高級複合物。熟習此項技術者藉由考慮本說明書及本文所揭示的實施例之實踐當可明瞭本發明之其他實施例。如本說明書及申請專利範圍中所使用，「一」及/或「一個」可指一個或超過一個。除非另有指示，否則無論是否存在術語「約」，用於本說明書及申請專利範圍中之所有表示成分之量、性質(諸如分子量)、百分比、比率、反應條件等等之數字在所有情況下均應理解為由術語「約」修飾。因此，除非有相反指示，否則本說明書及申請專利範圍中闡述的數字參數為可根據本發明企圖獲得的所需性質而改變之近似值。至少且不試圖將均等論之應用限制於申請專利範圍之範疇，各數字參數應至少根據所報導的有效數字之數目且藉由應用尋常捨入技術來理解。儘管闡述本發明之寬廣範疇之數字範圍及參數為近似值，但特定實例中闡述的數值係儘可能精確地報告。然而，任何數值均固有地包含由於在其各次測試測量中存在的標準偏差所必然導致之特定誤差。本說明書及實例意欲僅被視為是示例性，且本發明之真實範疇及精神由隨後的申請專利範圍指示。POM was successfully synthesized via iCVD by using 1,3,5-trioxane monomer and boron trifluoride initiator. The iCVD POM film is structured to result in a hydrophobic POM surface. By adjusting the iCVD process conditions of substrate temperature, reactor pressure and nitrogen flow rate, polymer growth, kinetics and morphology can be adjusted. Using the method of the present invention to facilitate dry synthesis and structuring of POM films can open up new application fields, including electronics, mechanical systems, barrier films, templated and advanced composites. Those skilled in the art can understand other embodiments of the present invention by considering the practice of this specification and the embodiments disclosed herein. As used in this specification and the scope of the patent application, "one" and/or "one" can refer to one or more than one. Unless otherwise indicated, regardless of the existence of the term "about", all figures used in this specification and the scope of the patent application that indicate the amounts, properties (such as molecular weight), percentages, ratios, reaction conditions, etc. of the ingredients are in all cases Both should be understood as modified by the term "about". Therefore, unless there are instructions to the contrary, the numerical parameters described in this specification and the scope of the patent application are approximate values that can be changed according to the desired properties that the present invention attempts to obtain. At least and not trying to limit the application of egalitarianism to the scope of the patent application, each numerical parameter should be understood at least based on the number of significant figures reported and by applying ordinary rounding techniques. Although the numerical ranges and parameters describing the broad scope of the present invention are approximate values, the numerical values set forth in the specific examples are reported as accurately as possible. However, any numerical value inherently contains a specific error inevitably caused by the standard deviation in each test measurement. This specification and examples are intended to be regarded as exemplary only, and the true scope and spirit of the present invention are indicated by the scope of subsequent patent applications.

前述實施例在實踐中容易發生顯著變化。因此，實施例無意受限於上文中闡述的特定實例。而是，前述實施例係在隨附申請專利範圍之精神及範疇內，包括根據法律可獲得的其等效物。在本領域中通常遇到且熟習此項技術者明白之各種條件及參數之其他適宜修改及調適係在本發明之範疇內。The foregoing embodiments are prone to significant changes in practice. Therefore, the embodiments are not intended to be limited to the specific examples set forth above. Rather, the foregoing embodiments are within the spirit and scope of the scope of the attached patent application, including their equivalents available under the law. Other suitable modifications and adaptations of various conditions and parameters that are commonly encountered in the art and understood by those familiar with the art are within the scope of the present invention.

本文引用的所有專利及公開案之全文或至少其描述之經具體引用或在本描述中仰賴之部分係以引用之方式完全併入本文中。The full texts of all patents and publications cited herein or at least the parts of their descriptions specifically cited or dependent in this description are fully incorporated herein by reference.

專利權人無意將任何所揭示的實施例奉獻給公眾，且在任何所揭示的修改或改動可不真正落入申請專利範圍之範疇內之程度上，其依均等論被認為是申請專利範圍之一部分。The patentee does not intend to dedicate any disclosed embodiment to the public, and to the extent that any disclosed modification or change does not really fall within the scope of the patent application, it is considered to be part of the scope of the patent application based on the theory of equality .

應明瞭，本文所揭示的各組分、化合物、取代基或參數應解釋為經揭示以單獨使用或與本文所揭示的每一其他組分、化合物、取代基或參數中之一者或多者組合使用。It should be understood that each component, compound, substituent or parameter disclosed herein should be interpreted as one or more of the components, compounds, substituents or parameters disclosed herein to be used alone or in combination with each other component, compound, substituent or parameter disclosed herein Used in combination.

亦應明瞭，本文所揭示的各組分、化合物、取代基或參數之各量/值或量/值之範圍應解釋為亦以與針對於本文所揭示的任何其他組分、化合物、取代基或參數揭示的各量/值或量/值之範圍組合方式揭示及本文所揭示的兩種或更多種組分、化合物、取代基或參數之量/值或量/值之範圍之任何組合因此亦針對於本描述之目的以彼此組合方式揭示。It should also be understood that the respective amounts/values or ranges of the amounts/values of each component, compound, substituent or parameter disclosed herein should also be construed as similar to any other components, compounds, substituents disclosed herein Or any combination of the amounts/values or ranges of the amounts/values disclosed by the parameters and any combination of the amounts/values or ranges of the amounts/values of two or more components, compounds, substituents or parameters disclosed herein Therefore, it is also disclosed in combination with each other for the purpose of this description.

亦應明瞭，本文所揭示的各範圍應解釋為在所揭示範圍內的具有相同數目之有效數字之各特定值之揭示內容。因此，1至4之範圍應解釋為值1、2、3及4之明確揭示內容。It should also be understood that each range disclosed herein should be interpreted as the disclosure of each specific value with the same number of significant figures within the disclosed range. Therefore, the range of 1 to 4 should be interpreted as the explicit disclosure of the values 1, 2, 3, and 4.

應進一步明瞭，本文所揭示的各範圍之各下限應解釋為以與本文針對於相同組分、化合物、取代基或參數揭示的各範圍之各上限及各範圍內之各特定值組合方式揭示。因此，本發明應解釋為藉由將各範圍之各下限與各範圍之各上限或與各範圍內之各特定值組合，或藉由將各範圍之各上限與各範圍內之各特定值組合得出所有範圍之揭示內容。It should be further understood that each lower limit of each range disclosed herein should be interpreted as a combination of each upper limit of each range and each specific value within each range disclosed herein for the same component, compound, substituent or parameter. Therefore, the present invention should be interpreted as by combining each lower limit of each range with each upper limit of each range or with each specific value within each range, or by combining each upper limit of each range with each specific value within each range Get all the scope of disclosure.

此外，揭示於本描述或一個實例中之組分、化合物、取代基或參數之特定量/值應解釋為某一範圍之下限或上限之揭示內容且因此可與本申請案其他地方揭示的相同組分、化合物、取代基或參數之某一範圍之任何其他下限或上限或特定量/值組合以形成該組分、化合物、取代基或參數之範圍。參考文獻 In addition, the specific amount/value of the component, compound, substituent or parameter disclosed in this description or an example should be interpreted as the disclosure of the lower limit or the upper limit of a certain range and therefore can be the same as disclosed elsewhere in this application Any other lower limit or upper limit or specific amount/value combination of a certain range of a component, compound, substituent or parameter to form the range of the component, compound, substituent or parameter. references

以下參考文獻可用於理解本文所論述的某些原理： 1. Mülhaupt, R.，Hermann Staudinger and the origin of macromolecular chemistry。Angewandte Chemie International Edition 2004 ， 43 (9)，1054-1063。 2. Staudinger, H.，Macromolecular Chemistry。In Nobel Lecture ，1953。 3. Baranowski, C. J.；Bahmanpour, A. M.；Kröcher, O.，Catalytic synthesis of polyoxymethylene dimethyl ethers (OME): A review。Applied Catalysis B: Environmental 2017 ， 217 ， 407-420。 4. Evans, S. M.；Keogh, P. S.，Wear mechanisms in polyoxymethylene spur gears.Wear 2019 ， 428-429 ，356-365。 5. Kongkhlang, T.；Tashiro, K.；Kotaki, M.；Chirachanchai, S.，Electrospinning as a New Technique To Control the Crystal Morphology and Molecular Orientation of Polyoxymethylene Nanofibers。Journal of the American Chemical Society 2008 ， 130 (46)，15460-15466。 6. Liu, D.；Zhang, S.；Cheng, H.；Peng, R.；Luo, Z.，Thermally Triggered Vanishing Bulk Polyoxymethylene for Transient Electronics。Scientific Reports 2019 ， 9 (1)，18107。 7. Loo, L. S.；Gleason, K. K.，Hot filament chemical vapor deposition of polyoxymethylene as a sacrificial layer for fabricating air gaps。Electrochemical and Solid-State Letters 2001 ， 4 (11)，G81-G84。 8. Lau, K. K.；Gleason, K. K.，Initiated chemical vapor deposition (iCVD) of poly (alkyl acrylates): a kinetic model。Macromolecules 2006 ， 39 (10)，3695-3703。 9. Lau, K. K.；Gleason, K. K.，Initiated chemical vapor deposition (iCVD) of poly (alkyl acrylates): an experimental study。Macromolecules 2006 ， 39 (10)，3688-3694。 10.    Bose, R. K.；Nejati, S.；Stufflet, D. R.；Lau, K. K. S.，Graft Polymerization of Anti-Fouling PEO Surfaces by Liquid-Free Initiated Chemical Vapor Deposition.Macromolecules 2012 ， 45 (17)，6915-6922。 11.    Hsieh, C.-Y.；Lau, K. K. S.，Growth of Polyglycidol in Porous TiO2 Nanoparticle Networks via Initiated Chemical Vapor Deposition: Probing Polymer Confinement Under High Nanoparticle Loading。Advanced Materials Interfaces 2015 ， 2 (17)，1500341-n/a。 12.    Hammick, D. L.；Boeree, A. R.，CCCXXIX.—Preparation of α-trioxymethylene and a new polymeride of formaldehyde。Journal of the Chemical Society ， Transactions 1922 ， 121 ，2738-2740。 13.    Weissermel, K.；Fischer, E.；Gutweiler, K.；Hermann, H.；Cherdron, H.，Polymerization of trioxane。Angewandte Chemie International Edition in English 1967 ， 6 (6)，526-533。 14.    Kern, W.；Jaacks, V.，Some kinetic effects in the polymerization of 1,3,5-trioxane。Journal of Polymer Science 1960 ， 48 (150)，399-404。 15.    Carazzolo, G.；Mammi, M.，Crystal structure of a new form of polyoxymethylene.Journal of Polymer Science Part A: General Papers 1963 ， 1 (3)，965-983。 16.    Kaelble, D.；Cirlin, E.，Dispersion and polar contributions to surface tension of poly (methylene oxide) and Na‐treated polytetrafluoroethylene。Journal of Polymer Science Part A‐2: Polymer Physics 1971 ， 9 (2)，363-368。The following references can be used to understand some of the principles discussed in this article: 1. Mülhaupt, R., Hermann Staudinger and the origin of macromolecular chemistry. Angewandte Chemie International Edition 2004 , 43 (9), 1054-1063. 2. Staudinger, H., Macromolecular Chemistry. In Nobel Lecture , 1953. 3. Baranowski, CJ; Bahmanpour, AM; Kröcher, O., Catalytic synthesis of polyoxymethylene dimethyl ethers (OME): A review. Applied Catalysis B: Environmental 2017 , 217 , 407-420. 4. Evans, SM; Keogh, PS, Wear mechanisms in polyoxymethylene spur gears. Wear 2019 , 428-429 , 356-365. 5. Kongkhlang, T.; Tashiro, K.; Kotaki, M.; Chirachanchai, S., Electrospinning as a New Technique To Control the Crystal Morphology and Molecular Orientation of Polyoxymethylene Nanofibers. Journal of the American Chemical Society 2008 , 130 (46), 15460-15466. 6. Liu, D.; Zhang, S.; Cheng, H.; Peng, R.; Luo, Z., Thermally Triggered Vanishing Bulk Polyoxymethylene for Transient Electronics. Scientific Reports 2019 , 9 (1), 18107. 7. Loo, LS; Gleason, KK, Hot filament chemical vapor deposition of polyoxymethylene as a sacrificial layer for fabricating air gaps. Electrochemical and Solid-State Letters 2001 , 4 (11), G81-G84. 8. Lau, KK; Gleason, KK, Initiated chemical vapor deposition (iCVD) of poly (alkyl acrylates): a kinetic model. Macromolecules 2006 , 39 (10), 3695-3703. 9. Lau, KK; Gleason, KK, Initiated chemical vapor deposition (iCVD) of poly (alkyl acrylates): an experimental study. Macromolecules 2006 , 39 (10), 3688-3694. 10. Bose, RK; Nejati, S.; Stufflet, DR; Lau, KKS, Graft Polymerization of Anti-Fouling PEO Surfaces by Liquid-Free Initiated Chemical Vapor Deposition. Macromolecules 2012 , 45 (17), 6915-6922. 11. Hsieh, C.-Y.; Lau, KKS, Growth of Polyglycidol in Porous TiO2 Nanoparticle Networks via Initiated Chemical Vapor Deposition: Probing Polymer Confinement Under High Nanoparticle Loading. Advanced Materials Interfaces 2015 , 2 (17), 1500341-n/a. 12. Hammick, DL; Boeree, AR, CCCXXIX.—Preparation of α-trioxymethylene and a new polymeride of formaldehyde. Journal of the Chemical Society , Transactions 1922 , 121 , 2738-2740. 13. Weissermel, K.; Fischer, E.; Gutweiler, K.; Hermann, H.; Cherdron, H., Polymerization of trioxane. Angewandte Chemie International Edition in English 1967 , 6 (6), 526-533. 14. Kern, W.; Jaacks, V., Some kinetic effects in the polymerization of 1,3,5-trioxane. Journal of Polymer Science 1960 , 48 (150), 399-404. 15. Carazzolo, G.; Mammi, M., Crystal structure of a new form of polyoxymethylene. Journal of Polymer Science Part A: General Papers 1963 , 1 (3), 965-983. 16. Kaelble, D.; Cirlin, E., Dispersion and polar contributions to surface tension of poly (methylene oxide) and Na-treated polytetrafluoroethylene. Journal of Polymer Science Part A-2: Polymer Physics 1971 , 9 (2), 363-368.

圖1顯示1,3,5-三噁烷之iCVD聚合之提出的引發反應機制。Figure 1 shows the proposed initiation reaction mechanism for the iCVD polymerization of 1,3,5-trioxane.

圖2顯示1,3,5-三噁烷單體(上圖)，及利用燈絲加熱(操作編號3；中間)及不利用燈絲加熱(操作編號2；下圖)合成之iCVD POM之傅立葉轉換紅外(FTIR)光譜。Figure 2 shows the Fourier transform of 1,3,5-trioxane monomer (above) and iCVD POM synthesized with filament heating (operation number 3; middle) and without filament heating (operation number 2; bottom image) Infrared (FTIR) spectroscopy.

圖3顯示iCVD POM之三角形晶體形式之六角形堆疊之X射線粉末繞射(XRD)光譜。Figure 3 shows the X-ray powder diffraction (XRD) spectrum of the hexagonal stack of triangular crystals of iCVD POM.

圖4A至4B、4D至4E及4G至4H顯示掃描電子顯微術(SEM)影像。Figures 4A to 4B, 4D to 4E, and 4G to 4H show scanning electron microscopy (SEM) images.

圖4C、4F及4I顯示來自操作編號3 (對應於圖4A至4C)、操作編號4 (對應於圖4G至4I)及操作編號7 (對應於圖4G至4I)之iCVD POM膜之水滴影像。對於圖4A、4D及4G，比例尺為10 µm及對於圖4B、4E及4H，為400 nm。Figures 4C, 4F and 4I show images of water droplets from the iCVD POM film of operation number 3 (corresponding to Figures 4A to 4C), operation number 4 (corresponding to Figures 4G to 4I), and operation number 7 (corresponding to Figures 4G to 4I) . For Figures 4A, 4D, and 4G, the scale bar is 10 µm and for Figures 4B, 4E, and 4H, it is 400 nm.

Claims (20)

一種用於在基板上合成聚甲醛之方法，該方法包括如下步驟： 在起始化學氣相沉積反應器中將能夠藉由起始聚合反應形成聚甲醛之單體及引發劑經由起始化學氣相沉積(iCVD)沉積至基板之表面上。A method for synthesizing polyoxymethylene on a substrate, the method includes the following steps: In the initial chemical vapor deposition reactor, monomers and initiators capable of forming polyoxymethylene through initial polymerization are deposited on the surface of the substrate through initial chemical vapor deposition (iCVD). 如請求項1之方法，其中將該基板冷卻以促進該單體及該引發劑在該基板上之沉積。The method of claim 1, wherein the substrate is cooled to promote the deposition of the monomer and the initiator on the substrate. 如請求項2之方法，其中將該基板冷卻至約0℃至約50℃、或約0°至約40℃、約10℃至約35℃或約15℃至約25℃之溫度。The method of claim 2, wherein the substrate is cooled to a temperature of about 0°C to about 50°C, or about 0° to about 40°C, about 10°C to about 35°C, or about 15°C to about 25°C. 如請求項1之方法，其中如使用壓力計(例如電容式壓力計)測得，該起始化學氣相沉積反應器中之內部反應器壓力為約0.1至約10托，或約0.5至約5托、或約1至約3托。The method of claim 1, wherein the internal reactor pressure in the initial chemical vapor deposition reactor is about 0.1 to about 10 Torr, or about 0.5 to about 5 Torr, or about 1 to about 3 Torr. 如請求項1之方法，其中該沉積步驟係以約0.1至約20標準立方厘米/分鐘(sccm)、或約2至約15 sccm、或約3至約10 sccm之單體流入該起始化學氣相沉積反應器之流速進行。The method of claim 1, wherein the deposition step is about 0.1 to about 20 standard cubic centimeters per minute (sccm), or about 2 to about 15 sccm, or about 3 to about 10 sccm of monomer flowing into the starting chemical The flow rate of the vapor deposition reactor is carried out. 如請求項1之方法，其中該引發劑係選自由三氟化硼合***(boron trifluoride diethyl etherate)、三氟化硼及其他三氟化硼錯合物組成之群，其他三氟化硼錯合物包括與水、苯酚、乙酸、四氫呋喃、甲醇、丙醇、乙胺、甲基硫醚及二丁醚錯合之三氟化硼。Such as the method of claim 1, wherein the initiator is selected from the group consisting of boron trifluoride diethyl etherate, boron trifluoride and other boron trifluoride complexes, and other boron trifluoride complexes. Compounds include boron trifluoride complexed with water, phenol, acetic acid, tetrahydrofuran, methanol, propanol, ethylamine, methyl sulfide and dibutyl ether. 如請求項1之方法，其中在將該引發劑進料至該起始化學氣相沉積反應器之前，將該引發劑加熱至30℃至50℃、或30℃至40℃、或約35℃之溫度。The method of claim 1, wherein before feeding the initiator to the initial chemical vapor deposition reactor, the initiator is heated to 30°C to 50°C, or 30°C to 40°C, or about 35°C的温度。 The temperature. 如請求項1之方法，其中該引發劑係以約0.1至10標準立方厘米/分鐘(sccm)、或約0.5至7.5 sccm、或約1至5 sccm之流速進料至該起始化學氣相沉積反應器。The method of claim 1, wherein the initiator is fed to the starting chemical gas phase at a flow rate of about 0.1 to 10 standard cubic centimeters per minute (sccm), or about 0.5 to 7.5 sccm, or about 1 to 5 sccm Deposition reactor. 如請求項1之方法，其中該基板係選自矽、玻璃、織物、紙、塑膠、藥品、金屬、金屬氧化物、離子液體，及包含結構化、模板化、機製及界定拓撲中之一者或多者之表面及裝置。The method of claim 1, wherein the substrate is selected from silicon, glass, fabric, paper, plastic, pharmaceuticals, metals, metal oxides, ionic liquids, and includes one of structuring, templating, mechanism, and defined topology Or more surfaces and devices. 如請求項1之方法，其中該沉積步驟係利用位於該起始化學氣相沉積反應器中之一或多個經加熱燈絲來進行。The method of claim 1, wherein the deposition step is performed using one or more heated filaments located in the initial chemical vapor deposition reactor. 如請求項10之方法，其中該一或多個燈絲為磷青銅燈絲導線。The method of claim 10, wherein the one or more filaments are phosphor bronze filament wires. 如請求項10之方法，其中將該燈絲加熱至150℃至400℃、或約200℃至約375℃、或約250℃至約350℃之溫度。The method of claim 10, wherein the filament is heated to a temperature of 150°C to 400°C, or about 200°C to about 375°C, or about 250°C to about 350°C. 如請求項1之方法，其中該方法進一步包括將氮氣引入至該反應器中之步驟。The method of claim 1, wherein the method further comprises the step of introducing nitrogen into the reactor. 如請求項13之方法，其中該氮氣係以0.1 sccm至約2 sccm、或約1 sccm之流速引入至該反應器中。The method of claim 13, wherein the nitrogen gas is introduced into the reactor at a flow rate of 0.1 sccm to about 2 sccm, or about 1 sccm. 如請求項1之方法，其中該單體係選自由1,3,5-三噁烷、甲醛、二噁烷、可形成甲醛及其寡聚物之其他環分子諸如較大(CH2 O)含環分子、及已知用於聚合反應中以形成聚甲醛之其他單體組成之群。The method of claim 1, wherein the single system is selected from 1,3,5-trioxane, formaldehyde, dioxane, other ring molecules that can form formaldehyde and its oligomers, such as larger (CH 2 O) A group of ring-containing molecules and other monomers known to be used in polymerization reactions to form polyoxymethylene. 如請求項1之方法，其中該沉積步驟係在使得該基板表面處1,3,5-三噁烷單體之分數飽和度(
Figure 03_image001
)通常介於0.1至約1之間之條件下進行，其中
Figure 03_image001
係由以下表達式定義：
Figure 03_image013
其中
Figure 03_image005
為該單體於氣相中之分壓，如基於透過精密針閥或質量流速控制器計量的組分流速及如透過壓力計(例如電容式壓力計)測得之反應器總壓力計算得，及
Figure 03_image015
為該基板表面處該單體之蒸氣壓，基於單體在如藉由表面溫度探針(例如接觸熱電偶)測得之基板溫度下之平衡蒸氣壓數據。The method of claim 1, wherein the deposition step is such that the fractional saturation of the 1,3,5-trioxane monomer at the surface of the substrate (
Figure 03_image001
) Is usually carried out under conditions between 0.1 and about 1, where
Figure 03_image001
Is defined by the following expression:
Figure 03_image013
in
Figure 03_image005
It is the partial pressure of the monomer in the gas phase, such as calculated based on the component flow rate measured by a precision needle valve or mass flow controller and the total pressure of the reactor as measured by a pressure gauge (such as a capacitive pressure gauge), and
Figure 03_image015
It is the vapor pressure of the monomer at the surface of the substrate, based on the equilibrium vapor pressure data of the monomer at the substrate temperature as measured by a surface temperature probe (such as a contact thermocouple). 如請求項1至16中任一項之方法，其中該方法進一步包括引入一或多種選自水、醇及醛之共反應物之步驟。The method according to any one of claims 1 to 16, wherein the method further comprises the step of introducing one or more co-reactants selected from water, alcohol and aldehyde. 如請求項17之方法，其中該共反應物為甲醇且該甲醇係以約0.1至約2 sccm、或約0.1至約1 sccm之流速引入至該反應器中。The method of claim 17, wherein the co-reactant is methanol and the methanol is introduced into the reactor at a flow rate of about 0.1 to about 2 sccm, or about 0.1 to about 1 sccm. 如請求項17之方法，其中該共反應物為多聚甲醛且該多聚甲醛係針對約0.1 sccm至約2 sccm、或約0.1 sccm至約2 sccm之蒸氣流速經熱加熱至60℃至120℃。The method of claim 17, wherein the co-reactant is paraformaldehyde and the paraformaldehyde is heated to 60° C. to 120° C. for a vapor flow rate of about 0.1 sccm to about 2 sccm, or about 0.1 sccm to about 2 sccm ℃. 如請求項1之方法，其中該方法進一步包括引入一或多種選自水之共反應物之步驟。The method of claim 1, wherein the method further comprises the step of introducing one or more co-reactants selected from water.
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